Circulatory process and apparatus for catalytically treating materials



June l?, 1924. 1,497,75l

E. HOPKlNSON CIRCULATORY PROCESS AN'D APPARATUS FOR CATALYTICALLY TREATING MATERIALS Filed April 17, 1923 Patented June 17, 19,24.

ERNEST HOPKINSON,

OF NEW YORK, N. Y.

CIRJCULATORY PROCESS AND APPARATUS FOR CATALYTICAL-LY TREATING MATERIALS.

Application filed April 17, 1923. Serial No. 632,599.

To all whom t may concern Be it known that l, ERNEST HormNsoN, a citizen of the United States, and residing at New York city, county of New York, and 5 State of New York, have invented certain new and useful Improvements in a Circulatory Process. and Apparatus for Catalytically Treating Materials, of which the tollowing is a full, clear, and exact description. l This invention relates to a circulatory process and apparatus for catalytically treating materials, more particularly as applied to the production-of carbon black.

The use of carbon black for many purl poses has become quite common, such as in the compounding of rubber, and in the making of printers ink and pigments` lVhile a number of methods are known for its manufacture, a large part of it has been obtained by the incomplete combustion of a hydroca bon, more particularly natural gas', the carbon being deposited from the flame by the interposltion of a cooling surface. This method is extremely wasteful, and only a very small percentage of the chemically combined carbon is obtained in the Iterm of carbon black. If a hydro-carbon is heated to a high enough temperature it can of course be dissociated into its elements` and as an example, methane, when heated to about 1200o C. under a pressure of one atmosphere, is practically completely separated into carbon and hydrogen, but the elevated temperature required and other ditliculties have prevented any extensive practical use of this method. It is known that the temperature required for this dissociation may be considerably reduced if the operation is conducted in the presence of certain catalytic agents, amen which are palladium black, platinum blac reduced nickel, cobalt, copper, zinc, and iron. For example, the aliphatic saturated hydro-carbons in the presence of these agents readily undergo decomposition and dissociation at temperatures as low as 300 and 400 C.; andthe action of platinum'black on acetylene is quite marked at 150 C. However, a difficulty in the use of such catalysts lies in the fact that they quickly vbecome coated with the carbon black, or else oiso'ned by various impuritie's such as su phur in the hydro-carbon so that in a very short time their catalytic effect ,lis greatly .reduced or entirely overcome. AThis"po1soning of catalysts in general by certain substances is a serious defect in their use.

An object of my invention is to provide a continuous or circulatory process 'for the treatment of materialsV by a finely divided catalyst. y

Another object is to provide a catalytic process for the treatment of materials by which clogging and slowing up of the action of the catalyst is avoided.

Another object of my invention is to provide a simple and effective process for obtaining carbon black.

Still another object is to provide an improved catalytic process for dissociating hydro-carbons.

A further object is to provide a substantially continuous carbon black process by which the hydro-carbon and catalyst after reaction are rapidly withdrawn from the zone of treatment, the products separated, and the catalyst disposed for further use.

/ A still 4further object is to provide a sim: ple and eiiicient apparatus for carrying out the process.

For a detailed disclosure of the nature and objects of the invention reference is had to the accompanying specification and drawing, in which latter the figure represents more or less diagrammatically one embodiment of an apparatus for carrying out the process as applied to the production or' carbon black.

Referring to the drawing, the numeral l designates any suitable form of heater, which is provided in the present instance with a gas burner 2, and above the burner 1s disposed a coil or other suitable arrangement Stor heating the hydro-carbon. LeadingT from the coil 3 is a discharge pipe 4 which extends for some distance into a y passage way or pipe 5 and terminates in a nozzle 4 within the latter, the pipe 5 being surrounded by any suitable form of electric heating element 6 for additionally heatin the hydro-carbon it necessary. The numera 7 designates a hopper to which may be .supplied any suitable catalyst in finely divlded condition, and the catalytic material is fed from this hopper by a screw conveyor 8 to a pipe 9 leading into the pipe 5 slightly 1n advance of the discharge nozzle for the heated hydro-carbon. If necessary the catalytic material may be supplied in a preheated condition, and the pipe 9 is also pro-` vided with an electric heating element 10 for further heatin the material if desired. Beyond the electric heating elements the ipe 5 leads into a tank orreceptaclell and its discharge end 12 is upwardly turned and slightly spaced from a relatively large baie plate 13 suspended within the tank. A washin and cooling material such as water is supp ied to the' tank 11 through the valve controlled pi e 14 in quantity sufficient to keep the 'ba e plate 13 submerged some. distance below the surface. The pipe 5 is preferably provided with a suitable check valve for preventing backward flow of' water from the tank 11. The tank 11 is also provided with a valve controlled outlet 15 for withdrawing the carbon and' water sludge, and below the latter with a second valve controlled outlet 16 for withdrawing the .catalytic material. Leading from the top of the tank is a ipe 17 for withdrawing the gaseous by-pro ucts such as hydrogen, and communicating with this pipe is a valve controlled pipe 18 which is connected to the gas burner 2 in the heater 1.

In carrying out the process -as applied to the making of carbon: black, any suitable carbon compound such as natural gas or a liquid hydro-carbon is supplied to the heating coil 3, from which it passes. into .the electrically heated pipe 4, the heating being governed so as to raise the temperature of the particular hydro-carbon used to an extent suflicient to cause its dissociation and dehydrogenation upon coming in contact with a suitable catalyst. The' catalyst, which may be reduced nickel, cobalt, copper, or other suitable material, is supplied to the hopper 7, and as before stated if necessary it may be pre-heated. is fed by the conveyor heated pipe From the hopper it 8 into the electrically 9, and finally discharged into -the heated Vpipe 5 adjacent the discharge the carbon is set free.

nozzle 4: for the heated hydro-carbon. The heating of the hydro-carbon and ,catalyst may be accomplished solely by the use of the gaseous by-products or in any other suitable manner. catalyst, which is intimately mingled in finely divided form withthe hydro-carbon,

If it should be attempted to pass hydro-carbon through a stationary mass or body of a. finely divided catalyst the carbon set free deposits on the catalyst and the latter quickly becomes clogged and ineffective. Moreover, certain substances such as sulphur which occur as v impurities in mineral hydro-carbons appear to have a detrimental effect on the catalyst and greatly reduce or impair its effect, which. action is technically known as poisoning. By the use of my process, however, a continuous stream of hydro-carbon is intimately mingled with and subjected to the action ol't a continuous stream of cata- Under the influence of the I lytic material, hence,

each molecule of the hydro-carbon -can be acted upon by freshly activated and clean catalytic material and i the discharge underwater in the tank 11.

The battle plate 13 aids in the washing and separating of the carbon and the catalytic material as the particles pass beneath it along with the gaseous by-products, which latter then bubble to the surface of the liquid and may be drawn off through pipe 17. The carbon black, being light, forms a sludge with the water which may be drawn ,off from time to time through the outlet 15. The metallic catalyst being heavier settles to the inclined bottom of the tank and may be withdrawn from time to time through the outlet 16 and dried or otherwise prepared for return to the hopper 7 and subsequent re-use.

It will be seen that by my invention there is practically a continuous circulation of the catalyst, each particle of which acts only for a limited time on the hydro-carbon, is then freed from any attached carbon, treated if necessary to remove any poisoning"l effect caused by material such as sulphur, etc., in the hydro-carbon, and then again starts on a newcycle. Owing to the i'api 4 expansion of the hydro-carbon as it is released from the discharge nozzle the hydrocarbon and catalytic material remain as before stated or only a very limited time in the heated reaction zone but are swept away from the saine and into the cooling and separating chamber or receptacle. By reason of this action the carbon set free from the hydro-carbon is not allowed to deposit in the heated reaction zone and thereby become hardened and agglomerated.

While a specific embodiment of the process and of an apparatus for carrying out the same have been disclosed, it is evident that numerous modifications will suggest themselves to those skilled in the art, and the invention is applicable to the catalytic treatment of various materials. I believe that I am the iirst to make use of a catalytic dissociation process and apparatus by which the catalytic material may be continuously circulated to avoid the previously known defects of clogging and poisoning, and I do not desire that the invention shall be limited otherwise than set forth in the appended claims.

Having thus described my invention, what I claim and desire to protect by Letters Patent is:

1. The circulatory process of catalytically dissociating materials which consists in intimately mingling the material and a cata- 1 stin -a reaction zone, rapidly withdrawing e mixturefrom 'said zone and separating the catalyst therefrom, and again mingling the catalyst witha further portion of the terial and a catalyst in a. finely divided condition in a reaction zone, rapidly and continuously withdrawing the mixture from said zone and separating the catalyst therefrom, treating the latter to reactivat'e it, and again mingling it with a further portion of the material.

3. The process of producing carbon black which comprises freeing the carbon from a carbon compound by contact with a finely divided catalyst at dissociation temperature, and continuously removing and separating the carbon and catalyst.

4. The process of producing carbon black which comprises subjecting a continuous stream of a carbon compound to a continu# ous stream of a catalyst .at dissociation temperature, and separating the freed carbon from the catalyst.

5. The process of producing carbon black which comprises subjecting a continuous stream of a carbon compound to a continuous stream of a catalyst at dissociation temperature, and separating the :treed carbon and catal st from the by-products by treatment wit water.

6. The process of producingcarbon black 4which comprises subjecting a continuous stream of a carbon compound to a continuous stream of a catalyst at dissociation temperature, separating the treed carbon and catalyst from the by products under water,

vand separating the carbon and catalyst by 7. he process of producing carbonv black which comprises mixing a carboncompound with a finely divided catalyst in, the presence of heat, continuousl removing the mixture, and-recovering t e freed carbon and the catalyst.

8. The process of producing carbon black which comprises intimatel mixin a carbon compound anda cata yst in t e presence of heat, continuously removing the resultant products from the heat zone, and recovering the Vcarbon black and catalyst from the same under water.`

9. The process of producing carbon black which comprises treating a carbon compound with a catalyst in suspension, remov-l ing the products, and separating the carbon and catalyst from the by products.

10. lThe process of producing carbon black which comprises treating a carbon 4compound with a. catalyst in suspension in the presence of heat, continu'ouslyremoving the resultant products from the heat zone, and separating the carbon and catalyst from the by products.

11. The process of producing carbon black which comprises preheating a lcarbon compound, preheating a catalyst, intimately mingling the latter in suspension vwith the carbon compound in the presence of heat, rapidly withdrawing the materials from the heat zone, and separating the by products, carbon and catalyst by a water treatment.

12. The continuous catalytic process of to dissociate the hydrocarbon, and means for separating the dissociation products of the hydrocarbon from each other and from the catalyst.

14. An apparatus for producing carbon black comprising means for continuously mingling a hydroecarbon and a finely divided catalyst, means for heating them adjacent the ri'iixing point, means for con-l ducting the'mixture from the mixing point, and means for recovering the catalyst and carbon from said mixture.

15. An apparatus for producin carbon black comprising a heated receptac e, means for dischargingpa heated carbon compound thereinto, means for supplyin `catalyst to the receptacle to m1-x with the carbon compound, means for withdrawing the mixture, and means for -washing and separating the catalyst, freed carbon and by products.

Signed .at- New York, county of New York, and State of New York, this 13th day of April, 1923.

ERNEST HOPKINSON.

a' heated 

